CN113471519B - Sulfide solid electrolyte diaphragm, precursor sol thereof and preparation method - Google Patents
Sulfide solid electrolyte diaphragm, precursor sol thereof and preparation method Download PDFInfo
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- CN113471519B CN113471519B CN202110727908.2A CN202110727908A CN113471519B CN 113471519 B CN113471519 B CN 113471519B CN 202110727908 A CN202110727908 A CN 202110727908A CN 113471519 B CN113471519 B CN 113471519B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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Abstract
The invention discloses a sulfide solid electrolyte diaphragm, precursor sol thereof and a preparation method thereof, wherein the preparation method of the sulfide solid electrolyte precursor sol comprises the steps of providing sol, wherein the components of the sol comprise Li 2 S; will P 2 S 5 And Li 2 S is added into an aprotic polar solvent to react to obtain a solution containing an intermediate compound or an emulsion containing the intermediate compound; and mixing the sol and the solution containing the intermediate compound or the emulsion containing the intermediate compound, and reacting to obtain the sulfide solid electrolyte precursor sol. The preparation method provided by the invention has the advantages of simple process, lower cost, short reaction time and high efficiency, and the prepared uniform and stable sulfide solid electrolyte precursor sol can be used for various common wet chemical membrane preparation methods to prepare ultrathin, compact, uniform and high-ionic conductivity sulfide solid electrolyte membranes.
Description
Technical Field
The invention relates to the field of solid batteries, in particular to a sulfide solid electrolyte diaphragm, a precursor sol thereof and a preparation method thereof.
Background
The all-solid-state lithium battery has the advantages of high energy/power density, good safety and the like, and is a novel secondary battery with great potential. The solid electrolyte diaphragm is used as a core component of the solid-state battery and plays roles in realizing positive and negative electrode ion transmission and blocking electron transmission. However, the solid electrolyte separator does not have an energy storage function, and an excessively thick separator would seriously reduce the overall energy density of the battery. Therefore, the ultra-thinning and densification of the solid electrolyte separator are key to the practical application of the all-solid lithium battery.
The sulfide solid electrolyte diaphragm has extremely high room temperature ionic conductivity equivalent to that of organic electrolyte, and the process temperature required by preparation and forming is lower (< 300 ℃), so that the sulfide solid electrolyte diaphragm is an ideal ion transmission material of the all-solid-state lithium battery.
Physical vapor deposition can be used to produce ultra-thin sulfide solid electrolyte membranes, e.g., non-patent literature Effect of processes Li 2 S on electrochemical properties of amorphous Li 3 PS 4 A physical vapor deposition technique for sulfide solid electrolyte ultra-thin membranes is disclosed in the Journal of American Ceramics Society,2017,100, 746. With Li 3 PS 4 The solid electrolyte is a target material, and the solid electrolyte diaphragm with the submicron thickness can be prepared by adopting a laser pulse deposition technology. The separator can be used for assembling a thin film lithium battery. However, the technology has high requirements on the diaphragm deposition equipment, not only is the diaphragm deposition equipment required to have high vacuum degree, but also the deposition cavity is required to be connected with an inert atmosphere device, the equipment structure is complex, and the maintenance cost is high.
The sulfide solid electrolyte is prepared by mechanical alloying methods such as high-energy ball milling and the like, and can also be used for preparing a sulfide solid electrolyte diaphragm by a powder cold pressing technology. However, the powder prepared by the method has coarse particles, and the particle size is generally more than tens of microns, so that the preparation of an ultra-thin diaphragm is difficult, and the compactness is low.
In order to reduce the particle size of sulfide solid electrolytes, researchers have recently conducted studies on their liquid phase synthesis techniques. For example, the non-patent document of sub-micrometer-thick electrolyte membranes of β -Li 3 PS 4 A liquid phase synthesis method for preparing Li is disclosed in via finished assembly of nanoscales, plate-like building blocks, advanced Energy Materials,2018,1800014 3 PS 4 Solid electrolyte nano-sheets, and further a technology for preparing ultrathin sulfide solid electrolyte membranes. Firstly, with Li 2 S and P 2 S 5 Synthesizing precursor particles in tetrahydrofuran as raw materials, adding acetonitrile, stripping the particles into nanosheets with the thickness of 80nm and the length and width of several microns through sol exchange, and forming a thin layer stacked by the nanosheets on a substrate through a pulling methodFinally, the thin layer is densified through hot-pressing sintering, and the solid electrolyte diaphragm with the thickness of 0.4-35 mu m is prepared. However, this method involves a hot-pressing sintering process, which increases the process complexity. Meanwhile, when a solid electrolyte diaphragm with the thickness of less than 1 mu m is prepared, the uniformity of the film layer is poor.
The wet chemical film-making method has simple equipment structure and process, and can be used for preparing the sulfide solid electrolyte diaphragm. In the conventional liquid-phase synthesis process of lithium thiophosphate solid electrolyte, the reaction raw material Li 2 S and P 2 S 5 Simultaneously adding the mixture into a solvent to stir for reaction, wherein in the process, a reactant Li 2 S and P 2 S 5 The solution is slightly soluble in a solvent, the reaction process is carried out at a solid-liquid interface, the reaction speed is slow, the particles of a reaction product are large (generally larger than 100 nm), the lithium thiophosphate solid electrolyte precursor obtained by the reaction is insoluble in the solvent, and the obtained lithium thiophosphate solid electrolyte precursor solution is turbid liquid and cannot be used for wet chemical membrane preparation.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a sulfide solid electrolyte diaphragm, a precursor sol thereof and a preparation method, and aims to solve the problem that sulfide solid electrolyte precursor particles prepared by the existing method are large and cannot be used for wet chemical membrane preparation.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for producing a sulfide solid electrolyte precursor sol, comprising the steps of:
providing a sol, the components of which include Li 2 S；
Will P 2 S 5 And Li 2 S is added into an aprotic polar solvent to react to obtain a solution containing an intermediate compound or an emulsion containing the intermediate compound;
and mixing the sol and the solution containing the intermediate compound or the emulsion containing the intermediate compound, and reacting to obtain the sulfide solid electrolyte precursor sol.
Optionally, the components of the sol further comprise soluble components selected from one or more of LiI, liCl, liBr.
Optionally, the P 2 S 5 And Li 2 S is added into an aprotic polar solvent for reaction, and the P 2 S 5 And Li 2 The molar ratio of S is 2.
Optionally, the aprotic polar solvent is selected from one or more of nitriles, esters, ethers.
Alternatively, li in the sol 2 S and said P 2 S 5 And Li 2 Li in reaction of S added into non-proton polar solvent 2 The sum of the number of moles of S and the sum of the number of moles of P 2 S 5 And Li 2 P in the reaction of S in aprotic polar solvent 2 S 5 The molar ratio of (a) to (b) is 70.
In a second aspect of the invention, a sulfide solid electrolyte precursor sol is provided, wherein the sulfide solid electrolyte precursor sol is prepared by the preparation method of the sulfide solid electrolyte precursor sol.
In a third aspect of the present invention, there is provided a method for producing a sulfide solid electrolyte membrane, comprising the steps of:
providing a substrate;
transferring the sulfide solid electrolyte precursor sol to the substrate, and drying in an inert atmosphere or in a vacuum state;
and then carrying out heat treatment in an inert atmosphere or in a vacuum state, and preparing the sulfide solid electrolyte membrane on the substrate.
The fourth aspect of the invention provides a sulfide solid electrolyte membrane, wherein the sulfide solid electrolyte membrane is prepared by the preparation method of the sulfide solid electrolyte membrane.
In a fifth aspect of the present invention, there is provided a method for producing a sulfide solid electrolyte, wherein,
drying the sulfide solid electrolyte precursor sol in an inert atmosphere or in a vacuum state, and then carrying out heat treatment in the inert atmosphere or in the vacuum state to obtain the sulfide solid electrolyte.
The sixth aspect of the invention provides a sulfide solid electrolyte, wherein the sulfide solid electrolyte is prepared by the preparation method of the sulfide solid electrolyte.
Has the advantages that: the preparation method provided by the invention has the advantages of simple process and low cost, the particles in the prepared sulfide solid electrolyte precursor sol belong to the nanometer grade, and the sulfide solid electrolyte precursor sol has uniform and stable properties and can be used for various common wet chemical membrane preparation methods, so that the ultrathin, compact and uniform sulfide solid electrolyte membrane with high ionic conductivity can be prepared.
Drawings
Fig. 1 is a flow chart of preparation of a sulfide solid electrolyte precursor sol according to an embodiment of the present invention.
FIG. 2 is an XRD spectrum of a lithium thiophosphate solid electrolyte in example 1 of the present invention.
FIG. 3 is an SEM photograph of a lithium thiophosphate solid electrolyte in example 1 of the present invention.
Fig. 4 is an XRD spectrum of the lithium thiophosphate solid electrolyte in example 2 of the present invention.
FIG. 5 is an XRD spectrum of a lithium thiophosphate solid electrolyte in example 3 of the present invention.
FIG. 6 is an XRD spectrum of a lithium thiophosphate solid electrolyte in example 4 of the present invention.
Fig. 7 is a cross-sectional SEM image of a lithium thiophosphate solid electrolyte thin film in example 5 of the present invention.
Fig. 8a is a diagram showing the result of the tyndall effect test of the sol of the lithium thiophosphate solid electrolyte precursor in example 1 of the present invention.
Fig. 8b is a diagram showing the result of the tyndall effect test of the sol of the lithium thiophosphate solid electrolyte precursor in example 2 of the present invention.
Fig. 8c is a diagram showing the result of the tyndall effect test of the sol of the lithium thiophosphate solid electrolyte precursor in example 3 of the present invention.
Detailed Description
The present invention provides a sulfide solid electrolyte membrane, a precursor sol thereof and a preparation method thereof, and the present invention is further described in detail below in order to make the objects, technical schemes and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In the conventional liquid-phase synthesis process of lithium thiophosphate solid electrolyte, reaction raw material Li 2 S and P 2 S 5 Simultaneously adding the mixture into a solvent to stir for reaction, wherein in the process, a reactant Li 2 S and P 2 S 5 The method is characterized in that the method is slightly soluble in a solvent, the reaction process is carried out at a solid-liquid interface, the reaction speed is slow, the particles of a reaction product are large (generally larger than 100 nm), the lithium thiophosphate solid electrolyte precursor obtained by the reaction is insoluble in the solvent, the obtained lithium thiophosphate solid electrolyte precursor solution is suspension liquid, the solution cannot be used for wet chemical membrane preparation, and a compact and ultrathin lithium thiophosphate solid electrolyte membrane cannot be prepared.
Based on this, an embodiment of the present invention provides a method for preparing a sulfide solid electrolyte precursor sol, as shown in fig. 1, wherein the method includes the steps of:
s11, providing a sol, wherein the components of the sol comprise Li 2 S；
S12, adding P 2 S 5 And Li 2 S is added into an aprotic polar solvent to react to obtain a solution containing an intermediate compound or an emulsion containing the intermediate compound;
and S13, mixing the sol and the solution containing the intermediate compound or the emulsion containing the intermediate compound, and reacting to obtain the sulfide solid electrolyte precursor sol.
In this example, preparationThe obtained sulfide solid electrolyte precursor sol is lithium thiophosphate solid electrolyte precursor sol, and specifically, the liquid phase synthesis process of the lithium thiophosphate solid electrolyte precursor is completed step by step to obtain the sol-state sulfide solid electrolyte precursor, namely, the lithium thiophosphate solid electrolyte sol. First, li is contained in the mixture 2 Sol of S (Li) 2 S is dispersoid), li in the sol 2 S is a nanoparticle, which can accelerate the reaction rate and contribute to the nanocrystallization of the lithium thiophosphate particles as the final product when reacting with the solution containing the intermediate compound or the emulsion containing the intermediate compound prepared in step S12, taking advantage of the large specific surface area of the nanoparticle. Then, li 2 S and P 2 S 5 Quickly reacting in non-protonic polar solvent to obtain solution or emulsion containing intermediate compound (Li) 2 S·P 2 S 5 Or Li 2 P 2 S 6 Or (LipS) 3 ) n Wherein n is a positive integer. Li 2 S and P 2 S 5 Can react rapidly in a plurality of aprotic polar solvents, while for a part of aprotic polar solvents, the intermediate compound Li 2 S·P 2 S 5 Or Li 2 P 2 S 6 Or (LipS) 3 ) n Soluble therein to form a solution, while for another part of the aprotic solvent, the intermediate compound Li 2 S·P 2 S 5 Or Li 2 P 2 S 6 Or (LipS) 3 ) n Insoluble therein to form an emulsion. Thus, P is 2 S 5 And Li 2 S is added into an aprotic polar solvent to react, and a solution containing an intermediate compound or an emulsion containing an intermediate compound can be obtained. Finally, by containing Li 2 And reacting the sol of S with a solution containing an intermediate compound or an emulsion containing the intermediate compound to prepare the lithium thiophosphate solid electrolyte precursor sol. Because the reactants of the reaction are in the state of sol, solution or emulsion, the reactants can be uniformly mixed, the reaction rate is greatly increased, and nano-scale product particles are easier to form, thereby obtaining the sulfurReplacing lithium phosphate solid electrolyte precursor sol.
The preparation method of the lithium thiophosphate solid electrolyte precursor sol provided by the embodiment has the advantages of simple process, low cost, short reaction time and high efficiency, and the reaction time can be greatly shortened from tens of hours of the conventional method to 1 hour.
The particles in the lithium thiophosphate solid electrolyte precursor sol in the embodiment belong to the nanometer scale (lithium thiophosphate solid electrolyte particles below 50nm can be prepared), and the lithium thiophosphate solid electrolyte precursor sol has uniform and stable properties and can be used for various common wet chemical membrane preparation methods. Compared with a non-sol type lithium thiophosphate solid electrolyte precursor suspension with large particles in the prior art, the particles in the lithium thiophosphate solid electrolyte precursor sol in the embodiment belong to a nanometer grade, and the lithium thiophosphate solid electrolyte precursor sol has the uniform and stable properties, so that the lithium thiophosphate solid electrolyte precursor sol in the embodiment can be used for preparing an ultrathin, compact and uniform lithium thiophosphate solid electrolyte diaphragm by a wet chemical membrane preparation method. In addition, in the prior art, some polysulfide is used as a reactant, so that the prepared lithium thiophosphate solid electrolyte precursor solution contains excessive sulfur, so that the lithium thiophosphate solid electrolyte membrane prepared by the lithium thiophosphate solid electrolyte precursor solution contains an elemental sulfur impurity phase, and the ion conductivity is low. In this embodiment, the reactant is Li-containing 2 The sol of S and the solution containing the intermediate compound or the emulsion containing the intermediate compound do not contain excessive sulfur in the reactant, and the lithium thiophosphate solid electrolyte precursor sol prepared by the preparation method of the embodiment does not contain excessive sulfur, so that the lithium thiophosphate solid electrolyte membrane prepared by the lithium thiophosphate solid electrolyte precursor sol provided by the embodiment does not contain elemental sulfur impurity phase, and has high ionic conductivity. Therefore, the lithium thiophosphate solid electrolyte precursor sol in the embodiment can be used for preparing ultrathin, compact and uniform sulfur without elemental sulfur impurity phase and with high ionic conductivity by a wet chemical membrane preparation methodA lithium phosphate solid electrolyte separator.
In step S11, in one embodiment, the Li is prepared by physical or chemical agglomeration 2 Sols of S, but not limited thereto, other for preparation including Li 2 The sol-gel method of S is also applicable to the present invention.
Physical or chemical agglomeration methods are methods in which molecules or ions are physically or chemically agglomerated into colloidal particles. The physical condensation method can be to prepare sol by utilizing the obvious difference of the solubility of substances in different solvents, and the two solvents are required to be completely miscible; the chemical coagulation method is a method in which a product is supersaturated by various chemical reactions, and insoluble fine particles produced at the beginning are combined into colloidal particles, and a sol is formed in the presence of a small amount of a stabilizer, which is generally a reactant in an excess amount.
For example, elemental sulfur is added to LiEt under an argon atmosphere using a chemical condensation method 3 In tetrahydrofuran solution of BH by reducing anionic group Et 3 BH - Rapidly reducing elemental S to S 2- Resulting in Li in solution 2 The concentration of S is sharply increased to trigger the explosive nucleation growth of the S to generate Li 2 And (3) S nanoparticles.
In one embodiment, preparing the sol further comprises the step of purifying the sol to remove reaction by-products by centrifugation, dialysis, or the like.
In one embodiment, the sol further comprises a soluble component selected from one or more of LiI, liCl, liBr.
In the present embodiment, doping modification of the lithium thiophosphate solid electrolyte precursor sol or generation of a new ionic conductivity phase such as a spodumene solid electrolyte precursor sol is realized by adding one or more soluble components of LiI, liCl, liBr, and the like, and the ionic conductivity of the lithium thiophosphate solid electrolyte can be further improved.
In step S12, in one embodiment, the P is added 2 S 5 And Li 2 S is added into an aprotic polar solvent to carry out a reaction,said P is 2 S 5 And Li 2 The molar ratio of S is (2). This ratio range can guarantee P 2 S 5 And Li 2 S reacts to the greatest extent to form a solution or emulsion containing the intermediate compound. The intermediate compound is dissolved in the aprotic polar solvent or forms an emulsion with the aprotic polar solvent, which is more favorable for L 2 S sol is mixed uniformly and is beneficial to L 2 The S sol reacts in a liquid phase, the reaction speed is high, and finally the lithium thiophosphate solid electrolyte precursor sol with small (nano) particles can be generated, so that the reactant Li in the prior art is avoided 2 S and P 2 S 5 Slightly soluble in solvent, the reaction process is carried out at a solid-liquid interface, the reaction speed is slow, and the particles of the reaction product are coarse.
In one embodiment, the aprotic polar solvent is selected from one or more of nitriles, esters, ethers. The nitrile may be selected from acetonitrile, but is not limited thereto; the ester may be selected from one or more of propyl acetate, ethyl formate, ethyl acetate, etc., but is not limited thereto; the ether may be selected from one or more of tetrahydrofuran, tetraglyme, ethylene glycol dimethyl ether, 1, 3-dioxolane, etc., but is not limited thereto. Will P 2 S 5 And Li 2 S is added into an aprotic polar solvent to react, and a solution containing an intermediate compound or an emulsion containing the intermediate compound can be obtained. In this embodiment, the intermediate compound may be dissolved in acetonitrile, propyl acetate, ethyl formate, ethyl acetate, tetraglyme, 1, 3-dioxolane to form a solution containing the intermediate compound, and the intermediate compound may be insoluble in tetrahydrofuran to form an emulsion containing the intermediate compound.
If solid-phase insoluble impurities are formed in the intermediate compound-containing solution or the intermediate compound-containing emulsion in step S12, they can be removed by filtration, i.e., in step S13, when the sol and the intermediate compound-containing solution or the intermediate compound-containing emulsion are mixed, in a preferred embodiment, the intermediate compound-containing solution or the intermediate compound-containing emulsion does not contain solid-phase insoluble impurities.
In steps S11 and S12, in one embodiment, li in the sol 2 S and said P 2 S 5 And Li 2 Li in reaction of S added into non-proton polar solvent 2 The sum of the number of moles of S and the sum of the number of moles of P 2 S 5 And Li 2 P in the reaction of S in aprotic polar solvent 2 S 5 The molar ratio of (a) to (b) is 70. That is to say in both S11 and S12 steps, li is added 2 Total number of moles of S and P 2 S 5 The ratio of the total number of moles is 70. The molar ratio can obtain the lithium thiophosphate solid electrolyte with higher ionic conductivity.
In step S13, in an embodiment, the solution containing the intermediate compound or the emulsion containing the intermediate compound is added dropwise to the sol in an inert gas atmosphere, and stirring is continued, so as to obtain a transparent or semitransparent lithium thiophosphate solid electrolyte precursor sol after reaction.
The embodiment of the invention also provides sulfide solid electrolyte precursor sol which is prepared by the preparation method of the sulfide solid electrolyte precursor sol.
The sulfide solid electrolyte precursor sol provided in the embodiment is lithium thiophosphate solid electrolyte precursor sol, has uniform and stable properties, has particles in the sol in a nanometer scale, can be used for preparing lithium thiophosphate solid electrolyte and a lithium thiophosphate solid electrolyte membrane through a humidification chemical membrane preparation method, and is compact and uniform, free of elemental sulfur impurity phase and high in ionic conductivity. In addition, the particles in the lithium thiophosphate solid electrolyte precursor sol are in a nanometer level, the nano particles have extremely high specific surface area, and a large number of surfaces with high reaction activity can obviously increase the sintering performance of the powder, so the sintering performance among the powder in the diaphragm can be increased.
Because the lithium thiophosphate solid electrolyte precursor sol provided by the embodiment of the invention can be used for preparing the lithium thiophosphate solid electrolyte diaphragm by a wet chemical method, the embodiment of the invention also provides a preparation method of the lithium thiophosphate solid electrolyte diaphragm, wherein the preparation method comprises the following steps:
s21, providing a substrate;
s22, transferring the lithium thiophosphate solid electrolyte precursor sol on the substrate, and drying in an inert atmosphere or in a vacuum state;
s23, performing heat treatment in an inert atmosphere or in a vacuum state, and preparing the lithium thiophosphate solid electrolyte membrane on the substrate.
The substrate in step S21 is not particularly limited in this embodiment, and a suitable substrate may be provided, and may be, for example, a high temperature resistant polymer such as glass and polyimide, or a metal that is not easily reacted with sulfide, but is not limited thereto. In addition, the lithium thiophosphate solid electrolyte in the embodiment can also be directly used for assembling the battery by taking the positive electrode or the negative electrode of the battery as a substrate.
In step S22, the lithium thiophosphate solid electrolyte precursor sol according to the embodiment of the present invention is transferred onto the substrate, and the lithium thiophosphate solid electrolyte precursor sol is prepared into a thin film by a wet film forming and drying method. The wet film forming method includes, but is not limited to, a pulling method and a spin coating method.
In one embodiment, the drying is performed by heating in an inert atmosphere or under vacuum.
In step S23, in one embodiment, the lithium thiophosphate solid electrolyte membrane is prepared on the substrate after heat treatment at 120 to 300 ℃ in an inert atmosphere or in a vacuum state.
The preparation method provided by the embodiment can be used for preparing the compact and uniform lithium thiophosphate solid electrolyte membrane which does not contain elemental sulfur impurity phase and has high ionic conductivity, and the thickness of the lithium thiophosphate solid electrolyte membrane can be adjusted, that is, the thickness of the lithium thiophosphate solid electrolyte membrane can be controlled by a wet chemical membrane preparation method, for example, the thickness of the lithium thiophosphate solid electrolyte membrane can be controlled by controlling the number of spin-coated layers by a spin coating method.
The embodiment of the invention also provides a lithium thiophosphate solid electrolyte diaphragm which is prepared by the preparation method of the lithium thiophosphate solid electrolyte diaphragm.
The lithium thiophosphate solid electrolyte membrane in the embodiment is compact and uniform, does not contain elemental sulfur impurity phase, and has high ionic conductivity.
The precursor sol of the lithium thiophosphate solid electrolyte described in the embodiment of the present invention can also be used for preparing the lithium thiophosphate solid electrolyte, and therefore, the embodiment of the present invention also provides a preparation method of the lithium thiophosphate solid electrolyte, wherein the precursor sol of the lithium thiophosphate solid electrolyte described in the embodiment of the present invention is dried in an inert atmosphere or in a vacuum state, and then is subjected to heat treatment in the inert atmosphere or in the vacuum state, so as to obtain the lithium thiophosphate solid electrolyte. The lithium thiophosphate solid electrolyte is in a powder state.
The particle size of the lithium thiophosphate solid electrolyte prepared in this example is 50nm or less.
In one embodiment, the lithium thiophosphate solid electrolyte precursor sol according to the embodiment of the present invention is dried by heating in an inert atmosphere or under a vacuum state, and then is heat-treated at 120 to 300 ℃ in an inert atmosphere or under a vacuum state, so as to prepare the lithium thiophosphate solid electrolyte.
The embodiment of the invention also provides a lithium thiophosphate solid electrolyte, wherein the lithium thiophosphate solid electrolyte is prepared by the preparation method of the lithium thiophosphate solid electrolyte.
In the present embodiment, the lithium thiophosphate solid electrolyte is nanoparticles having a particle size of 50nm or less, and can increase the contact with other components when used in a solid composite positive electrode.
The invention is further illustrated by the following specific examples.
Example 1
Under an argon atmosphere, 4mmol of elemental sulfur were added to 8mL of LiEt 3 LiEt with a molar BH concentration of 1mol/L 3 Continuously stirring in tetrahydrofuran solution of BH until the reaction is completed, removing reaction by-product after high-speed centrifugation, and then obtaining Li 2 S is dispersed in 30mL of tetrahydrofuran to obtain Li 2 The concentration of S is 0.1 mol/L. Under an argon atmosphere, 1.25mmol of P 2 S 5 With 1.25mmol of Li 2 S was added to 12.5mL acetonitrile and stirring was continued until a clear solution was obtained. 25mL of the above sol was taken and kept under stirring, and 12.5mL of the clear solution was added dropwise to the above sol, so that Li in the mixed solution came from the sol 2 S and Li from the clear solution 2 The sum of the moles of S and P from the clear solution 2 S 5 The ratio of the number of moles of (a). After the stirring is continued for 1 hour, a transparent lithium thiophosphate solid electrolyte precursor sol is obtained, and the tyndall effect test result of the transparent lithium thiophosphate solid electrolyte precursor sol is shown in fig. 8a, which proves that the transparent lithium thiophosphate solid electrolyte precursor sol prepared in the embodiment is obtained.
And drying the lithium thiophosphate precursor sol for 1h at 60 ℃ under the protection of argon, and carrying out heat treatment on the obtained powder for 1h at 250 ℃ in an argon atmosphere of 0.04MPa to obtain the lithium thiophosphate solid electrolyte. The XRD pattern is shown in figure 2, and from figure 2, the lithium thiophosphate solid electrolyte contains beta-Li 3 PS 4 And thio-LISICON II. The SEM image is shown in fig. 3, and it can be seen from fig. 3 that the lithium thiophosphate solid electrolyte is a nanoparticle having a particle size of about 30nm and has a uniform particle size. The ionic conductivity of the lithium thiophosphate solid electrolyte measured by an alternating current impedance method is 3.9 multiplied by 10 -5 S/cm。
Example 2
Under an argon atmosphere, 4mmol of elemental sulfur were added to 8mL of LiEt 3 LiEt with a molar BH concentration of 1mol/L 3 Continuously stirring in tetrahydrofuran solution of BH until the reaction is completed, removing reaction by-product after high-speed centrifugation, and then obtaining Li 2 S is dispersed in 30mL of tetrahydrofuran to obtain Li 2 The concentration of S is 0.1 mol/L. Under an argon atmosphere, 0.875mmol of P 2 S 5 With 0.875mmol of Li 2 S was added to 12.5mL of acetonitrile and stirring was continued until a clear solution was obtained. 25mL of the above sol was taken and kept under constant stirring, and 12.5mL of the clear solution was added dropwise to the sol to allow Li from the sol in the mixed solution 2 S and Li from the clear solution 2 The sum of the moles of S and P from the clear solution 2 S 5 The ratio of the number of moles of (a). After stirring for 1 hour, the transparent lithium thiophosphate solid electrolyte precursor sol is obtained, and the tyndall effect test result is shown in fig. 8b, which proves that the lithium thiophosphate solid electrolyte precursor sol prepared in the embodiment is obtained.
And drying the lithium thiophosphate precursor sol for 1h at 60 ℃ under the protection of argon, and carrying out heat treatment on the obtained powder for 1h at 250 ℃ in an argon atmosphere of 0.04MPa to obtain the lithium thiophosphate solid electrolyte. The XRD pattern is shown in FIG. 4, and it can be seen from FIG. 4 that the lithium thiophosphate solid electrolyte contains beta-Li 3 PS 4 And thio-lithium ion secondary battery, and Li is remained in the lithium thiophosphate solid electrolyte 2 And S. The ionic conductivity of the lithium thiophosphate solid electrolyte measured by an alternating current impedance method is 1.4 multiplied by 10 -5 S/cm。
Example 3
Under an argon atmosphere, 4mmol of elemental sulfur were added to 8mL of LiEt 3 LiEt with a molar BH concentration of 1mol/L 3 Continuously stirring in tetrahydrofuran solution of BH until the reaction is completed, removing reaction by-product after high-speed centrifugation, and then obtaining Li 2 S is dispersed in 30mL of tetrahydrofuran to obtain Li 2 The concentration of S is 0.1 mol/L. Under an argon atmosphere, 1.625mmol of P 2 S 5 With 1.625mmol of Li 2 S was added to 12.5mL acetonitrile and stirring was continued until a clear solution was obtained. 25mL of the above sol was taken and kept under constant stirring, and 12.5mL of clear solution was added dropwise to the sol, allowing Li from the sol in the mixed solution 2 S and Li from the clear solution 2 The sum of the moles of S and P from the clarified solution 2 S 5 The ratio of moles of (a) of (b) of 71.7. After further stirring for 1h, transparent thio-radicals are obtainedThe tyndall effect test result of the lithium phosphate solid electrolyte precursor sol is shown in fig. 8c, which proves that the lithium thiophosphate solid electrolyte precursor sol prepared in the embodiment is obtained.
And drying the lithium thiophosphate precursor sol for 1h at the temperature of 60 ℃ under the protection of argon, and carrying out heat treatment on the obtained powder for 1h at the temperature of 250 ℃ in the atmosphere of argon at the pressure of 0.04MPa to obtain the lithium thiophosphate solid electrolyte. The XRD pattern is shown in FIG. 5, and it can be seen from FIG. 5 that the lithium thiophosphate solid electrolyte contains beta-Li 3 PS 4 And Li 4 P 2 S 6 Two crystalline phases. The ionic conductivity of the lithium thiophosphate solid electrolyte measured by an alternating current impedance method is 1.3 multiplied by 10 -5 S/cm。
Example 4
Under the argon atmosphere, 10mmol of metal Li and 10mmol of naphthalene are added into 10mL of ethylene glycol dimethyl ether, and the mixture is stirred until the reaction is completed to form a Li-naphthalene solution. 1mmol of Li 2 S and 5mmol S powder are added into 10mL THF and stirred to obtain 0.1mol/L Li 2 S 6 Dropping the solution into the Li-naphthalene solution, and centrifuging to obtain 0.13mol/L Li 2 And (5) dissolving the sol. Under an argon atmosphere, 1.3mmol of P 2 S 5 With 1.3mmol of Li 2 S was added to 12mL of acetonitrile and stirring was continued until a clear solution was obtained. 20mL of the above sol was taken and kept under constant stirring, and 12mL of the clear solution was added dropwise to the sol, so that Li in the mixed solution came from the sol 2 S and Li from the clear solution 2 The sum of the moles of S and P from the clear solution 2 S 5 The ratio of the number of moles of (a). And continuously stirring for 1h to obtain transparent lithium thiophosphate solid electrolyte precursor sol.
And drying the lithium thiophosphate precursor sol at 60 ℃ under the protection of argon, and carrying out heat treatment on the obtained powder for 1h at 250 ℃ in an argon atmosphere of 0.04MPa to obtain the lithium thiophosphate solid electrolyte. The XRD pattern is shown in FIG. 6, and it can be seen from FIG. 6 that the lithium thiophosphate solid electrolyte contains beta-Li 3 PS 4 A crystalline phase. The ionic conductivity of the lithium thiophosphate solid electrolyte measured by an alternating current impedance method is 3.1×10 -5 S/cm。
Example 5
And (3) dripping 100 mu L of the lithium thiophosphate precursor sol prepared in the embodiment 1 onto the glass substrate treated by gold spraying, spin-coating to form a film by a spin coater at the rotating speed of 4000rpm/min, and carrying out heat treatment at 250 ℃ for 2h under the protection of inert atmosphere to obtain the lithium thiophosphate film. The above process can be repeatedly implemented, and the regulation and control of the thickness of the film are realized. The cross-sectional SEM image of the lithium thiophosphate solid electrolyte membrane having a thickness of about 550nm obtained after repeating the above process 10 times is shown in fig. 7, and it can be seen from fig. 7 that the lithium thiophosphate solid electrolyte membrane is dense and uniform. The lithium thiophosphate solid electrolyte diaphragm has the ion conductivity characteristic, and the resistance per unit area is only 0.75 omega cm -2 。
In summary, the present invention provides a sulfide solid electrolyte membrane, a precursor sol thereof, and a method for preparing the same, wherein first, a solid electrolyte membrane containing Li is prepared 2 The sol of S nanoparticles, taking advantage of the large specific surface area of nanoparticles, contributes to the acceleration of the reaction rate and to the nanocrystallization of the final product particles. Then, li 2 S and P 2 S 5 Can react rapidly in a variety of aprotic polar solvents to form solutions or emulsions containing intermediate compounds. Finally by containing Li 2 And reacting the sol of S with a solution containing an intermediate compound or an emulsion containing the intermediate compound to prepare the sulfide solid electrolyte precursor sol. Because the reactants of the reaction are in a sol, solution or emulsion state, the reactants can be uniformly mixed, the reaction rate is greatly increased, and nano-scale product particles are more easily formed, so that the sulfide solid electrolyte precursor sol is obtained. The preparation method of the sulfide solid electrolyte precursor sol provided by the invention has the advantages of short reaction time and high efficiency, and the reaction time can be greatly shortened from tens of hours of the conventional method to 1 hour. The particles in the sulfide solid electrolyte precursor sol belong to the nanometer grade (sulfide solid electrolyte particles below 50nm can be prepared), excessive sulfur is not contained, and the sulfide solid electrolyte precursor sol has uniform and stable properties and can be used for various common wet electrolyteThe sulfide electrolyte diaphragm which is ultrathin, compact and uniform, does not contain elemental sulfur impurity phase and has high ionic conductivity is further prepared by the chemical film preparation method.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a sulfide solid electrolyte precursor sol is characterized by comprising the following steps:
providing a sol, the components of which include Li 2 S；
Will P 2 S 5 And Li 2 S is added into an aprotic polar solvent to react to obtain a solution containing an intermediate compound or an emulsion containing the intermediate compound; the intermediate compound is Li 2 S·P 2 S 5 、Li 2 P 2 S 6 Or (LipS) 3 ) n, wherein n is a positive integer; mixing the sol and the solution containing the intermediate compound or the emulsion containing the intermediate compound, and reacting to obtain the sulfide solid electrolyte precursor sol; the sulfide solid electrolyte precursor sol is lithium thiophosphate solid electrolyte precursor gel;
li in the sol 2 And S is a nanoparticle.
2. The method according to claim 1, wherein the composition of the sol further comprises a soluble component selected from one or more of LiI, liCl, liBr.
3. The method for producing a sulfide solid electrolyte precursor sol according to claim 1, wherein the step of adding P is performed by 2 S 5 And Li 2 S is added into an aprotic polar solvent to carry out a reaction, and the P 2 S 5 And Li 2 The molar ratio of S is 2.
4. The method according to claim 1, wherein the aprotic polar solvent is selected from one or more of nitriles, esters, and ethers.
5. The method according to claim 1, wherein Li in the sol is added to the solution 2 S and said P 2 S 5 And Li 2 Li in reaction of S added into non-proton polar solvent 2 The sum of the number of moles of S and the sum of the number of moles of P 2 S 5 And Li 2 S is added into an aprotic polar solvent to carry out P in the reaction 2 S 5 The ratio of the molar numbers of (a) to (b) is 70.
6. A sulfide solid electrolyte precursor sol characterized by being prepared by the method for preparing a sulfide solid electrolyte precursor sol according to any one of claims 1 to 5.
7. A method for preparing a sulfide solid electrolyte membrane, comprising the steps of:
providing a substrate;
transferring the sulfide solid electrolyte precursor sol of claim 6 onto the substrate, and drying in an inert atmosphere or under a vacuum state;
and then carrying out heat treatment in an inert atmosphere or in a vacuum state, and preparing the sulfide solid electrolyte membrane on the substrate.
8. A sulfide solid electrolyte membrane produced by the method for producing a sulfide solid electrolyte membrane according to claim 7.
9. A preparation method of sulfide solid electrolyte is characterized in that,
drying the sulfide solid electrolyte precursor sol of claim 6 in an inert atmosphere or in a vacuum state, and then performing heat treatment in an inert atmosphere or in a vacuum state to obtain the sulfide solid electrolyte.
10. A sulfide solid electrolyte prepared by the method for preparing a sulfide solid electrolyte according to claim 9.
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| JPH10139436A (en) * | 1996-11-12 | 1998-05-26 | Tosoh Corp | Zirconia particle for solid electrolyte and its production |
| JP2004139859A (en) * | 2002-10-18 | 2004-05-13 | Nippon Soda Co Ltd | Solid electrolyte |
| CN104011926A (en) * | 2011-11-02 | 2014-08-27 | I-Ten公司 | Method for the production of thin films of solid electrolyte for lithium ion batteries |
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| US11271245B2 (en) * | 2017-03-22 | 2022-03-08 | Mitsubishi Gas Chemical Company, Inc. | Production method for solid electrolyte having Li3PS4 |
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| CN104011926A (en) * | 2011-11-02 | 2014-08-27 | I-Ten公司 | Method for the production of thin films of solid electrolyte for lithium ion batteries |
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